Process for dyeing wool with reactive dyes

ABSTRACT

There is disclosed a process for producing non-skittery and level dyeings on wool with reactive dyes in the presence of an auxiliary combination, which process comprises dyeing wool with an aqueous liquor consisting of at least one reactive dye and an auxiliary combination comprising, as component (a), at least one compound of formula ##STR1## and, as component (b), at least one compound of formula ##STR2## wherein R 1  and R 2  are each independently of the other an aliphatic radical of 12 to 24 carbon atoms, 
     Q and Q&#39; are each independently of the other C 1  -C 4  alkyl, --CH 2  --CO--NH 2 , ##STR3## A.sup.⊖  and A&#39;.sup.⊖  are an anion, Z 1 , Z 2 , Z&#39; 1  and Z&#39; 2  are each independently of one another hydrogen, SO 3  M or PO 3  M, 
     wherein M is hydrogen, alkali metal or ammonium, t 1  and t 2  are 1 or 0, when t 1  and t 2  are O, Z 1 , Z 2 , Z&#39; 1  and Z&#39; 2  are hydrogen or one of Z 1 , Z 2 , Z&#39; 1  and Z&#39; 2  is hydrogen and the other is SO 3  M or PO 3  M, m 1 , n 1 , p 1  and q 1  are integers, the sum of (m 1  +n 1 ) being 2 to 15 and that of (p 1  +q 1 ) being 25 to 200, and finishing the dyeing, irrespective of the depth of shade, in the pH range from 4.0 to 5.0. 
     The dyeing process of this invention gives non-skittery and level dyeings, especially in light to medium shades of good light- and wetfastness properties.

The present invention relates to a novel process for producingnon-skittery and level dyeings on wool with reactive dyes, to thematerial dyed by said novel process, and to a formulation for carryingout said process.

In U.S. Pat. No. 4 444 564 it is taught to dye natural polyamide fibresin the fibre preserving pH range. However, it is only possible toproduce dark shades satisfactorily for dyeing with reactive dyes bymeans of this process.

Surprisingly, a novel process has now been found which makes it possibleto obtain non-skittery and level dyeings, in light to medium shades, onwool with reactive dyes in the fibre preserving pH range.

Specifically, the present invention relates to a process for producingnon-skittery and level dyeings on wool with reactive dyes in thepresence of an auxiliary combination, which process comprises dyeingwool with an aqueous liquor consisting of at least one reactive dye andan auxiliary combination comprising, as component (a), at least onecompound of formula ##STR4## and, as component (b), at least onecompound of formula ##STR5## wherein R₁ and R₂ are each independently ofthe other an aliphatic radical of 12 to 24 carbon atoms,

Q and Q' are each independently of the other C₁ -C₄ alkyl, --CH₂--CO--NH₂, ##STR6## A.sup.⊖ and A'.sup.⊖ are an anion, Z₁, Z₂, Z'₁ andZ'₂ are each independently of one another hydrogen, SO₃ M or PO₃ M,wherein M is hydrogen, alkali metal or ammonium, t₁ and t₂ are 1 or 0,when t₁ and t₂ are 0, Z₁, Z₂, Z'₁ and Z'₂ are hydrogen or one of Z₁, Z₂,Z'₁ and Z'₂ is hydrogen and the other is SO₃ M or PO₃ M, m₁, n₁, p₁ andq₁ are integers, the sum of (m₁ +n₁) being 2 to 15 and that of (p₁ +q₁)being 25 to 200, and finishing the dyeing, irrespective of the depth ofshade, in the pH range from 4.0 to 5.0.

The present invention is especially suitable for producing light tomedium shades.

Preferred auxiliary combination components of formulae (1a) and (1b) arethose in which the sum of (m₁ +n₁) is 5 to 12 and that of (p₁ +q₁) is 25to 100.

The auxiliary combination may additionally comprise, as component (c), anonionic compound of formula ##STR7## wherein R" is an alkyl or alkenylradical of 12 to 22 carbon atoms and x and y are integers, the sum of xand y being 80 to 140.

It is preferred to use auxiliary combinations comprising, as component(a), a compound of formula ##STR8## and, as component (b), at least onecompound of formula ##STR9## and, as component (c), a compound offormula (2), wherein R₃ and R₄ are each independently of the other analiphatic radical of 12 to 24 carbon atoms,

Q₁ and Q'₁ are each independently of the other C₁ -C₄ alkyl or --CH₂--CO--NH₂,

Z₃, Z₄, Z'₃ and Z'₄ are each independently of the other SO₃ M,

M is hydrogen, alkali metal or ammonium,

m₂, n₂, p₂ and q₂ are integers, the sum of (m₂ +n₂) being 5 to 12 andthat of (p₂ +q₂) being 25 to 100, and

A₁.sup.⊖ and A₂.sup.⊖ are an anion.

A further preferred auxiliary combination comprises, as component (a), acompound of formula ##STR10## and, as component (b), a compound offormula ##STR11## wherein R₅ and R₆ are each independently of the otheran aliphatic radical of 12 to 24 carbon atoms,

Z₅ and Z₆ are hydrogen or one of Z₅ and Z₆ is hydrogen and the other isSO₃ M,

Z'₅ and Z'₆ are each independently of the other hydrogen or SO₃ M,

M is hydrogen, alkali metal or ammonium, and

m₃, n₃, p₃ and q₃ are integers, the sum of (m₃ +n₃) being 5 to 12 andthat of (p₃ +q₃) being 25 to 100.

Further preferred auxiliary combinations are those in which component(a) is a compound of formula (3a) and component (b) is a compound offormula (4b), or auxiliary combinations in which component (a) is acompound of formula (3b) and component (b) is a compound of formula(4a).

M in formulae (1), (3) and (4) is hydrogen, alkali metal such as sodiumor potassium, and, preferably, ammonium. The radicals Q, Q', Q₁ and Q'₁as well as A.sup.⊖, A'.sup.⊖, A₁.sup.⊖ and A₂.sup.⊖ in formulae (1) and(3) are derived from quaternising agents in which Q is C₁ -C₄ alkyl,--CH₂ --CO--NH₂, ##STR12##

Illustrative examples of such quaternising agents are acetyl bromide,ethyl bromide, ethylene chlorohydrin, ethylene bromohydrin,epichlorohydrin, epibromohydrin, dimethyl sulfate, diethyl sulfate and,preferably, chloroacetamide.

Suitable aliphatic radicals R₁, R₂, R₃, R₄, R₅ and R₆ in formulae (1),(3) and (4) are alkyl or alkenyl radicals of 12 to 24, preferably 16 to22, carbon atoms. Such radicals are typically n-dodecyl, myristyl,n-hexadecyl, n-heptadecyl, n-octadecyl, arachidyl, behenyl, dodecenyl,hexadecenyl, oleyl and octadecenyl.

The compounds of components (a), (b) and (c) are disclosed in U.S. Pat.No. 4,444,564.

The compounds of component (a) of formula (1a) are prepared by additionof 2 to 15 mol of ethylene oxide to aliphatic amines which contain analiphatic radical of 12 to 24 carbon atoms, and in further optionalsteps, converting the adduct into the acid monoester and then the acidmonester into the alkali or ammonium salt, or reacting the adduct withone of the above quaternising agents. The compounds of component (b) offormula (1b) are prepared by addition of 25 to 200 ml of ethylene oxideto aliphatic amines which contain an aliphatic radical of 12 to 24carbon atoms, and in further optional steps, converting the adduct intothe acid ester and then acid ester into the alkali or ammonium salt, orreacting the adduct with one of the above quaternising agents.

The compounds of formula (2) are prepared by addition of 80 to 140 molof ethylene oxide to a compound of formula ##STR13## wherein R" is asdefined for formula (2).

The starting amines required for the preparation of the compounds offormulae (1), (3) and (4) may be saturated or unsaturated, branched orunbranched hydrocarbon radicals of 12 to 24, preferably 16 to 22, carbonatoms. The amines can be chemically homogeneous or are in the form ofmixtures. Mixtures of amines are preferably those formed upon theconversion of natural fats or oils such as tallow oil, soybean oil orcoconut oil into the corresponding amines. Specific amines are typicallydodecylamine, hexadecylamine, octadecylamine, arachidylamine,behenylamine and octadecenylamine. A mixture of C₁₈ -C₂₂ fatty aminesand tallow fatty amine is preferred. Tallow fatty amine is a mixture ofca. 30% of hexadecylamine, 25% of octadecylamine and 45% ofoctadecenylamine.

The addition of ethylene oxide as well as the esterification can becarried out by methods known per se. Esterification can be carried outwith sulfuric acid or functional derivatives thereof such aschlorosulfonic acid and, preferably, sulfamic acid,

The esterification is normally carried out by simple mixing of thereactants, with heating, conveniently to a temperature in the range from50° to 100° C. The free acids can subsequently be converted into thealkali metal salts or ammonium salts by addition in conventional mannerof a base such as ammonia, sodium hydroxide or potassium hydroxide.

In the process of this invention, the auxiliary combination usedcomprises 10 to 80 parts, preferably 20 to 70 parts, of component (a), 5to 70 parts, preferably 5 to 50 parts, of component (b), and 0 to 70parts, preferably 0 to 50 parts of the compound of component (c), andwater to make up 100 parts.

The amounts in which the auxiliary combination comprising components(a), (b) and optionally (c) are added to the dyebath vary from 0.5 to 4percent by weight, based on the material to be dyed. It is preferred touse 1 to 2 percent by weight of the auxiliary combination, based on thematerial.

The weight ratio of component (a) to component (b) is from 1:5 to 10:1,preferably from 1:2 to 5:1.

Suitable fibre material for dyeing by the process of this invention iswool. The material can be in a wide range of presentation, for exampleflocks, yarn, woven fabrics, knitted fabrics or carpets. The wool canhave a normal or nonfelting finish.

Reactive dyes suitable for dyeing wool which has a normal or nonfeltingfinish by the process of this invention are the organic dyes known bythis term-irrespective of the nature of their reactive groups.

This class of dyes is listed under "Reactive Dyes" in the Colour Index,3rd Edition, 1971. They are predominantly dyes which contain at leastone group which reacts with polyhydroxyl (cellulose) fibres or polyamidefibres, especially wool, a precursor of such a group, or a substituentwhich reacts with polyhydroxyl (cellulose) fibres or polyamide fibres.

Particularly suitable reactive dyes are those selected from the seriesof the monoazo, disazo or polyazo dyes, including the formazan dyes, aswell as of the anthraquinone, xanthene, nitro, triphenylmethane,naphthoquinonimine, dioxazine and phthalocyanine dyes. The azo andphthalocyanine dyes can be metallised as well as non-metallised.

Illustrative examples of reactive groups and precursors which form suchreactive groups are epoxy groups, the ethylenimide group, the vinylgroup in vinylsulfone or in the acrylic acid radical, as well as theβ-sulfatoethylsulfone group, the β-chloroethylsulfone group or theβ-dialkylaminoethylsulfone group.

Reactive substituents of reactive dyes are those which are readilyremovable and leave behind an electrophilic radical.

Suitable substituents of this kind are typically 1 or 2 halogen atoms inan aliphatic acyl radical, for example in β-position or in α- andβ-position of a propionyl radical, or in α-and/or β-position of anacrylic acid radical, or 1 or 3 halogen atoms on the following ringsystems: pyridazine, pyrimidine, pyridazone, triazine, quinoxaline orphthalazine.

It is also possible to use dyes containing two or more identical ordifferent reactive groups.

Preferred reactive dyes contain chloroacetyl, bromoacroyl ordibromopropionyl as reactive substituents.

The reactive dyes can contain acid salt-forming substituents such ascarboxyl groups, sulfuric acid ester and phosphoric acid ester groups,phosphonic acid groups or, preferably, sulfo groups.

Preferred reactive dyes are those which contain at least one sulfogroup, preferably reactive dyes of the azo or anthraquinone type whichpreferably contain two or three sulfo groups.

Mixtures of reactive dyes can also be used, in which case bichromaticand trichromatic dyeings can be produced.

Dyeing is carried out by the exhaust process. The amount of dye added tothe dye liquor will depend on the desired colour strength. Amounts of0.01 to 10 percent by weight, preferably 0.01 to 2 percent by weight,based on the weight of the fibre material, have generally been founduseful.

The liquor ratio may be chosen within a wide range, typically from 1:3to 1:100, preferably from 1:8 to 1:30.

The dyebaths may contain mineral acids such as sulfuric acid orphosphoric acid, organic aicds, preferably aliphatic carboxylic acidssuch as formic acid, acetic acid, oxalic acid or citric acid, and/orsalts such as ammonium acetate, ammonium sulfate or sodium acetate. Theacids are used in particular to adjust the pH of the liquor, which is inthe range from 4 to 5.

The dye liquors may contain further ingredients, such as wool protectiveagents, dispersants amd wetting agents as well as antifoams.

The process of this invention does not require special apparatus. Theconventional dyeing machines such as open baths and machines for dyeingslubbing, hanks or packages, jiggers, paddle dyeing machines, beamdyeing machines, circulating liquor or jet dyeing machines orwinchbecks, can be used.

Dyeing is conveniently carried out in the temperature range from 60° to120° C., preferably from 70° to 105° C. The dyeing time is within normallimits and is ordinarily from 20 to 120 minutes.

Upon completion of dyeing, the dyeing process may be followed by anaftertreatment with alkali, typically with aqueous ammonia, an alkalimetal hydroxide, an alkali metal carbonate or hydrogencarbonate orhexamethylenetriamine. The pH of the alkali-containing dyebath isconveniently in the range from 7.5 to 9, preferably from 8 to 8.5.

Dyeing of the fibre material is conveniently carried out by brieflytreating the goods with an aqueous liquor which contains the acid andthe auxiliary combination comprising components (a) and (b) andoptionally (c), and which has a temperature of 30°-60° C., and addingthe reactive dye to the same bath. The temperature is then slowly raisedso as to be able to dye in the temperature range from 80°-100° C. for 20to 90 minutes, preferably for 30 to 60 minutes. The dyed goods are thentreated, as required after the addition of alkali, preferably sodiumhydrogencarbonate or sodium carbonate, for 10 to 20 minutes at 70°-90°C. Finally, the dyed material is removed from the bath and rinsed,acidified and dried in conventional manner.

The invention further relates to the auxiliary combination whichcomprises, as component (a), 10 to 80 parts of the compound of formula##STR14## as component (b), 5 to 70 parts of the compound of formula##STR15## wherein R₁ and R₂ are each independently of the other analiphatic radical of 12 to 24 carbon atoms,

Q and Q' are each independently of the other C₁ -C₄ alkyl, --CH₂--CO--NH₂, ##STR16## A.sup.⊖ and A'.sup.⊖ are an anion, Z₁, Z₂, Z'₁ andZ'₂ are each independently of one another hydrogen, SO₃ M or PO₃ M,

wherein M is hydrogen, alkali metal or ammonium, t₁ and t₂ are 1 or 0,when t₁ and t₂ are 0, Z₁, Z₂, Z'₁ and Z'₂ are hydrogen or one of Z₁, Z₂,Z'₁ and Z'₂ is hydrogen and the other is SO₃ M or PO₃ M, m₁, n₁, p₁ andq₁ are integers, the sum of (m₁ +n₁) being 2 to 15 and that of (p₁ +q₁)being 25 to 200, and, as component (c), 0 to 70 parts of the compound offormula (2) ##STR17## wherein R" is an alkyl or alkenyl radical of 12 to22 carbon atoms, and x and y are integers, the sum of x and y being 80to 140.

The dyeing process of this invention gives non-skittery and leveldyeings, especially in light to medium shades of good light- andwetfastness properties.

The invention is illustrated by the following Examples in which partsand percentages are by weight.

EXAMPLE 1

40 g of woollen fabric are treated for 10 minutes at 40° C. in acirculating liquor machine by the beam dyeing method. The liquorconsists of

4 g of sodium sulfate sicc.

0.8 g of sodium acetate

2 g of 80% acetic acid

800 ml of water

0.4 g of the auxiliary combination A₁ consisting of

a) 50 parts of the polyadduct of 7 mol of ethylene oxide with 1 mol oftallow fatty amine, quaternised with chloroacetamide, and

b) 50 parts of the ammonium salt of the monosulfated polyadduct of 7 molof ethylene oxide with 1 mol of tallow fatty amine, and

0.2 g of the auxiliary B₂ consisting of the polyadduct of 40 mol ofethylene oxide with 1 mol of a C₂₀ -C₂₂ fatty amine.

The pH of the liquor is 4.5.

After addition of a solution which contains 12 mg of the dye of formula##STR18## 24 mg of the dye of formula ##STR19## and 44 mg of the dye offormula ##STR20## the dye liquor is kept for ca. 5 minutes at 40° C. andthen heated to 60° C. at a rate of 1° C./min and kept at thistemperature for 20 minutes. The liquor is then heated to 98° C. at arate of 1° C./min and dyeing is carried out for 30 minutes. The liquoris cooled to 70° C. and the dyed goods are rinsed in conventionalmanner. A non-skittery and level dyeing of good fastness properties isobtained.

EXAMPLE 2

The procedure of Example 2 is repeated, using in place of the auxiliaryB₂

0.4 g of the auxiliary combination B₁ consisting of

a) 25.2 parts of the ammonium salt of the sulfated polyadduct of 8 molof ethylene oxide with 1 mol of tallow fatty amine,

b) 21.3 parts of the polyadduct of 34 mol of ethylene oxide with 1 moleof a C₂₀₋₂₂ fatty amine, quaternised with dimethyl sulfate, and

c) 7.0 parts of the compound of formula ##STR21## a non-skittery andlevel dyeing of good fastness properties is obtained.

EXAMPLE 3

The procedure described in Example 1 is repeated, using in place of theauxiliary B₂ 0.2 g of the polyadduct of 34 mol of ethylene oxide with 1mol of a C₂₀₋₂₂ fatty amine. A non-skittery and level dyeing of goodfastness properties is obtained.

EXAMPLE 4

The procedure described in Example 1 is repeated, in place of theauxiliary B₂ 0.2 g of the quaternised polyadduct of 34 mol of ethyleneoxide with 1 mol of a C₂₀₋₂₂ fatty amine. A non-skittery and leveldyeing of good fastness properties is obtained.

EXAMPLE 5

The procedure described in Example 1 is repeated, using in place of theauxiliary B₂ 0.2 g of the polyadduct of 30 mol of ethylene oxide with 1mol of tallow fatty amine. A non-skittery and level dyeing of goodfastness properties is obtained.

EXAMPLE 6

1 kg of worsted spun yarn in cheese form is pretreated for 15 minutes ina circulating liquor machine with 9 l of water of 40° C.,

100 g of sodium sulfate

9 g of ammonium acetate

37 ml of 80% acetic acid

9 g of a nonionic wetting agent based on 2-ethylhexanol

10 g of the auxiliary combination A₁

10 g of the auxiliary combination B₁

The pH of the liquor is 4.65. After addition of a solution whichcontains 0,3 g of the dye of formula (101), 0.6 g of the dye of formula(102) and 1.1 g of the dye of formula (103), the liquor is heated to 60°C. at a rate of 1° C./min and kept at this temperature for 20 minutes.The liquor is then heated at a rate of 1° C./min and dyeing is carriedout for 30 minutes. The liquor is cooled to 70° C. and the dyed goodsare rinsed in conventional manner. If required, the fastness propertiescan be enhanced by an aftertreatment with alkali, for example withammonia, sodium carbonate or sodium hydrogencarbonate. Non-skittery andlevel dyeings of excellent fastness properties are obtained.

EXAMPLE 7

The procedure described in Example 7 is repeated, using a dye solutioncomprising

4 g of the dye of formula (101)

6 g of the dye of formula (102), and

4 g of the dye of formula (103).

EXAMPLE 8

The procedure of Example 6 is repeated, using in place of the auxiliarycombinations of A₁ and B₁ 30 g of the auxiliary combination C₁ of thefollowing composition:

a) 5 parts of the polyadduct of 34 mol of ethylene oxide with 1 mol of aC₂₀₋₂₂ fatty amine, quaternised with dimethyl sulfate,

b) 2 parts of the compound of formula (104)

c) 20 parts of the polyadduct of 7 mol of ethylene oxide with 1 mol oftallow fatty amine, quaternised with chloroacetamide,

d) 20 parts of the ammonium salt of the monosulfated polyadduct of 7 molof ethylene oxide with 1 mol of tallow fatty amine, and

e) 2 parts of the polyadduct of 80 mol of ethylene oxide with 1 mol ofoleyl alcohol.

A non-skittery level dyeing of good fastness properties is obtained.

EXAMPLE 9

The procedure of Example 2 is repeated, using in place of the dyemixture 80 mg of the dye of formula ##STR22##

EXAMPLE 10

The procedure of Example 9 is repeated, using in place of 80 mg of thedye of formula (105) 80 mg of the dye of formula ##STR23##

EXAMPLE 11

The procedure of Example 9 is repeated, using in place of 80 mg of thedye of formula (105) 200 mg of the dye of formula ##STR24##

EXAMPLE 12

The procedure of Example 9 is repeated, using in place of 80 mg of thedye of formula (105) 320 mg of the dye of formula ##STR25##

EXAMPLE 13

The procedure of Example 9 is repeated, using in place of 80 mg of thedye of formula (105) 100 mg of the dye of formula ##STR26##

What is claimed is:
 1. A process for producing non-skittery and leveldyeings on wool with reactive dyes in the presence of an auxiliarycombination, which process comprises dyeing wool with an aqueous liquorconsisting of at least one reactive dye and an auxiliary combinationcomprising, as component (a), at least one compound of formulaand, ascomponent (b), at least one compound of formula ##STR27## wherein R₁ andR₂ are each independently of the other an alkyl or alkenyl radical of 12to 24 carbon atoms, Q and Q' are each independently of the other C₁ -C₄alkyl, --CH₂ --CO--NH₂, ##STR28## A.sup.⊖ and A'.sup.⊖ are an anion, Z₁,Z₂, Z'₁ and Z'₂ are each independently of one another hydrogen, SO₃ M orPO₃ M,wherein M is hydrogen, alkali metal or ammonium, t₁ and t₂ are 1or 0, when t₁ and t₂ are 0, Z₁, Z₂, Z'₁ and Z'₂ are hydrogen or one ofZ₁, Z₂, Z'₁ and Z'₂ is hydrogen and the other is SO₃ M or PO₃ M, m₁, n₁,p₁ and q₁ are integers, the sum of (m₁ +n₁) being 2 to 15 and that of(p₁ +q₁) being 25 to 200, and finishing the dyeing, irrespective of thedepth of shade, in the pH range from 4.0 to 5.0.
 2. A process accordingto claim 1, wherein the wool is dyed in light to medium shades.
 3. Aprocess according to claim 1, wherein the sum of (m₁ +n₁) is 5 to 12 andthat of (p₁ +q₁) is 25 to
 100. 4. A process according to claim 1,wherein the auxiliary combination additionally comprises, as component(c), a nonionic comound of formula ##STR29## wherein R" is an alkyl oralkenyl radical of 12 to 22 carbon atoms, and x and y are integers, thesum of x and y being 80 to
 140. 5. A process according to claim 1, whichcomprises the use of an auxiliary combination wherein component (a) is acompound of formula ##STR30## and component (b) is a compound of formula##STR31## and component (c) is a compound of formula (2), wherein R₃ andR₄ are each independently of the other an alkyl or alkenyl radical of 12to 24 carbon atoms,Q₁ and Q'₁ are each independently of the other C₁ toC₄ alkyl or --CH₂ --CO--NH₂, Z₃, Z₄, Z'₃ and Z'₄ are each independentlyof the other SO₃ M, M is hydrogen, alkali metal or ammonium, m₂, n₂, p₂and q₂ are integers, the sum of (m₂ +n₂) being 5 to 12 and that of (p₂+q₂) being 25 to 100, and A₁.sup.⊖ and A₂.sup.⊖ are an anion.
 6. Aprocess according to claim 1, which comprises the use of an auxiliarycombination wherein component (a) is a compound of formula ##STR32## andcomponent (b) is a compound of formula ##STR33## wherein R₅ and R₆ areeach independently of the other an alkyl or alkenyl radical of 12 to 24carbon atoms,Z₅ and Z₆ are hydrogen or one of Z₅ and Z₆ is hydrogen andthe other is SO₃ M, Z'₅ and Z'₆ are each independently of the otherhydrogen or SO₃ M, M is hydrogen, alkali metal or ammonium, and m₃, n₃,p₃ and q₃ are integers, the sum of (m₃ +n₃) being 5 to 12 and that of(p₃ +q₃) being 25 to
 100. 7. A process according to claim 1, whichcomprises the use of an auxiliary combination wherein component (a) is acompound of formula ##STR34## and component (b) is a compound of formula##STR35## wherein R₃ and R₆ are each independently of the other an alkylor alkenyl radical of 12 to 24 carbon atoms,Q₁ is C₁ to C₄ alkyl or--CH₂ --CO--NH₂, Z₃, Z₄, are each independently of the other SO₃ M, Z'₅and Z'₆ are each independently of the other hydrogen or SO₃ M, M ishydrogen, alkali metal or ammonium, m₂, n₂, p₃ and q₃ are integers, thesum of (m₂ +n₂) being 5 to 12, and that of (p₃ +q₃) being 25 to 100 andA₁.sup.⊖ is an anion.
 8. A process according to claim 1, which comprisesthe use of an auxiliary combination wherein component (a) is a compoundof formula ##STR36## and component (b) is a compound of formula##STR37## wherein R₄ and and R₅ are each independently of the other analkyl or alkenyl radical of 12 to 24 carbon atoms,Q'₁ is C₁ to C₄ alkylor --CH₂ --CO--NH₂, Z'₃ and Z'₄ are each independently of the other SO₃M, Z₅ and Z₆ are hydrogen or one of Z₅ and Z₆ is hydrogen and the otheris SO₃ M, M is hydrogen, alkali metal or ammonium, m₃, n₃, p₂ and q₂ areintegers, the sum of (m₃ +n₃) being 5 to 12 and that of (p₂ +q₂) being25to 100, and A₂.sup.⊖ is an anion.
 9. A process according to claim 1,which comprises the use of an auxiliary combination consisting of10 to80 parts of component (a) 5 to 70 parts of component (b), and 0 to 70parts of componente (c) and water to make up 100 parts.
 10. A processaccording to claim 1, wherein the weight ratio of component (a) tocomponent (b) is from 1:5 to 10:1.
 11. A process according to any one ofclaims 1, which comprises the use of reactive dyes which contain atleast one sulfo group.
 12. A process according to claim 11, whichcomprises the use of reactive dyes which contain chloroacetyl,bromoacetyl or dibromopropionyl.
 13. A process according to claim 1,wherein dyeing is carried out in the temperature range from 60° to 120°C.
 14. A process according to claim 1, wherein dyeing is carried out ata liquor ratio of 1:3 to 1:100, preferably from 1:8 to 1:30.
 15. Theauxiliary combination comprising, as component (a), 10 to 80 parts ofthe compound of formula ##STR38## as component (b), 5 to 70 parts of thecompound of formula ##STR39## wherein R₁ and R₂ are each independentlyof the other an alkyl or alkenyl radical of 12 to 24 carbon atoms,Q andQ' are each independently of the other C₁ -C₄ alkyl, --CH₂ --CO--NH₂,##STR40## A.sup.⊖ and A'.sup.⊖ are an anion, Z₁, Z₂, Z'₁ and Z'₂ areeach independently of one another hydrogen, SO₃ M or PO₃ M,wherein M ishydrogen, alkali metal or ammonium, t₁ and t₂ are 1 or 0, when t₁ and t₂are 0, Z₁, Z₂, Z'₁ and Z'₂ are hydrogen or one of Z₁, Z₂, Z'₁ and Z'₂ ishydrogen and the other is SO₃ M or PO₃ M, m₁, n₁, p₁ and q₁ areintegers, the sum of (m₁ +n₁) being 2 to 15 and that of (p₁ +q₁) being25 to 200, and, as component (c), 0 to 70 parts of the compound offormula (2) ##STR41## wherein R" is an alkyl or alkenyl radical of 12 to22 carbon atoms, and x and y are integers, the sum of x and y being 80to
 140. 16. The fibre material dyed by a process as claimed in claim 1.